Fumaric acid-conjugated hydrocarbon adducts



Patented June 29, 1948 FUMARIC ACID-CONJUGATED HYDRO- CARBON ADDUOTS Leslie C. Lane and Charles H. Parker, ford, Conn., assignorl to American Jr., Stam- Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application July 17, 1945, Serial No. 605.638

8 Claims. (Cl. 260-514) This invention relates to the preparation of adducts from fumaric acid and conjugated dienes. More particularly the invention relates to the preparation of fumaric acid adducts which are highly desirable in the production of improved resins.

The formation of adducts from certain ,5 unsaturated dicarboxylic acids and conjugated dienes is well known in the art. Numerous examples in the literature show the formation of adducts from maleic acid or its anhydride and conjugated dienes. It is to be observed that there is a conspicuous absence of examples showing an adduct formation wherein fumaric acid is the 1,5 unsaturated acid even though very frequently it is stated in literature that fumaric acid may be substituted for maleic acid or its anhydride to yield equivalent results. Statements are further made to allege that fumaric acid is converted into maleic anhydride by heating. These allegations have been found to be contrary to fact and there is no evidence to support the theory of equivalency or the conversion of fumaric acid into maleic acid or its anhydride when used in adduct formation under the described conditions. Experimental results proved the contrary to be true, that is, fumaric acid does not react the same as the maleic compound in adduct preparations and there is an absence of a conversion from fumaric acid to maleic acid or its anhydride when treated with heat under the conditions described.

Heretoiore, fumaric acid found little or no use in the production of adducts with conjugated dienes for subsequent utilization such as in the preparation of alkyd resins. This lack of utility has been the result of the failure to discover a suitable method for the formation of fumaricacid-conjugated diene adducts economical manner.

An object of this invention is to prepare adducts from fumaric acid and conjugated dienes.

Another object of this invention is to prepare adducts which are useful in the manufacture of in an efiicient and resins.

A further object is to prepare fumarlc acidconjugated diene adducts which are especially useful in the manufacture of improved alkyd resins.

These and other objects are attained as herein described.

According to the present invention, adducts are efliciently prepared by heating fumaric acid and a. conjugated diene in an aqueous medium. The preferred method for carrying out the reaction is achieved by the use of an autoclave accom- .panied by agitation but other methods may be used satisfactorily but with less efliciency, such as, for example, refluxing the mixture which requires considerabl more time to effect a complete addition. Best results are obtained when the addition reaction takes place in a closed vessel where the temperature of the reactant mixture is held within the 100 C. to 200 C. range for about a period of from to 90 minutes. However, the process is not restricted to the use of any definite reaction time, temperature or pressure.

If desired, there may be incorporated into the reaction mixture a stabilizer to prevent polymerization. Among other stabilizers, hydroquinone serves this purpose well when used in as little amounts as 0.02% based upon the weight of the diene used. Emulsiiiers may also be used when desired to improve adduct formation when the conjugated diene is very insoluble in water, such as, for example, alloiicimene.

The utility of the adducts may be directed to various arts such as the preparation of resins by reaction with polyhydric alcohols, which in turn are suitable for use in lacquers, varnishes, and various coating compositions. Such resins also find use in sizing, water-proofing and creaseproofing of textiles as well as in the production of filaments, threads in the fields of casting and 30 molding. The resins may be used in admixture with other natural or synthetic resins with or without the use of dyes, pigments, lubricants, catalysts, fillers and the like. The resins obtained by the use of the adducts of this invention are highly desirable for utilization in printing inks since they exhibit cardinal prerequisites of ink vehicles such as high gloss, good mineral spirits solubility, fast drying and good pigment wetting properties. The adducts are very desirable in the manufacture of alkyd resins for they not only fulfill the requirements of a substitute for phthalic anhydride in the large scale manufacture of alkyd resins, but go beyond such utility in yielding resins whose properties are superior to those obtained by the use of phthalic compounds. It

is not common for air-dried alkyd resins to exhibit mar-proof properties but the resins prepared with the adducts of this invention consistently show such properties, which is an important contribution in the advancement of the art. Resins employing the new adducts in their preparation also exhibit superior color retention after subjection to baking. This paves the way for improvements in the field of baked enamels and other finishes such as in the furniture and automotive indusmaleic acid during the process of adduct iormation. The monohydric alcohol esters of the adducts disclosed herein are useful as plasticizers for resinous substances.

Some of the conjugated dienes which form adducts with fumaric acid are: butadiene, isoprene, piperylene, B-myrcene, allodcimene, cyclopentadiene and the like. The dienes may be used individually or inadmixture with one or more dlenes. In the preparation of the adducts other reactants may be included such as hydroxy or poly-hydroxy organic compounds such as glycols, poly glycols, giycerols, pentaerythritol, mannitol, sorbitol, mono and di-glycerides and the like. Derivatives of hydroxy compounds may also be used to-. modify the properties of the alkyds. Among others'J'suitable modifiers areriatty oil glycerides, glyc rol monoaikyl ethers, and polyglycerol ethers, the aliphatic or aromatic acids, such as, fatty oil acids, phthalic acid, sebacic acid, stearic acid, oleic acid, and linoleic acid. Drying and non-drying oils may be also used as modifiers, such as linseed oil, walnut oil, tung oil, castor oil, and the like.

The following examples are given as a means of illustration and not in limitation. The term parts.'. as used throughougthe specification refers to parts-by weight. Varioust deviations may be made without departing from he spirit and scope of the invention.

Example 1 7 Parts Isoprene-piperylene mixture (20% inert hydrocarbons) 5'78 Fumaric acid 638 Water 825 The above materials are charged into an autoclave. The autoblave is then closed and heated at about 125 C. for about 90 minutes with agitation. A water-soluble adduct is formed giving a 90% yield.

The materials are charged into an autoclave. The autoclave is closed and heated at about 125 C. for about hour with agitation. I A watersoluble product is formed giving a yield of about 96%.

Example 3- Parts Isoprene (20% inert hydrocarbons) 580 Fumaric acid 640 Water 840 Hydroquinone The materials are charged into an autoclave. The autoclave is closed and heated at about 125 C. for about 1 hour with agitation. After purification and dehydration the yield of adduct is Example 4 Parts Isoprene (20% inert hydrocarbons) 5'18 Fumaric acid 638 Water 825 Hydroquinone 2 The above materials are charged into an autoclave. The autoclave is closed, and heated at about 125 C. for hour with agitation. The solution is steam distilled, filtered and vacuum concentrated to yield a white crystalline product.

Example 5 I Parts Alloiicimene (5% inert hydrocarbons) 340 Fumaric acid 290 Water 500 The above materials are charged into an autoclave. The autoclave is closed and heated at about 200 C. for a period of about /2 hour with agitation. The product is a crystalline solid.

The above materials are charged into an autoclave. The autoclave is closed and heated at about 150 C. for a period of about V hour with agitation. The product is a crystalline solid.

Example 7 Fum-aric acid is reacted with butadiene. for about /2 hour at about 200 C. The product is washed with benzene to yield a white solid.

Resin .4"

Parts 40 Isoprene-iumaric acid adduct 184 efined linseed monoglyceride 243 Glycerol 32 The above materials are charged into a kettle and heated at about 220 C. until the desired viscosity and acid number are obtained. Sixty parts of the product are dissolvedin 40 parts 0! mineral spirits giving an acid number of 14 and a viscosity of 37 poises. An air-dried film of the resin is mar-proof and shows good flexibility.

Upon'baking at about 150 C. for about /2 hour a hard film results which shows excellent color retention along with other desirable properties.

The above materials are charged into a kettle and heated at about 220C. until the desired acid number and viscosity are obtained. Seventy-five parts of product are dissolved in 25 parts of mineral spirits to give a viscosity of 18 poises and an acid number of 4. The solution is flowed out on a panel to give an air-dried film having good properties of flexibility, color and hardness. Upon baking for about a half hour the film has excellent hardness and color retention.

Resin "0" Parts Isoprene-fumaric adduct 18$ Linseed-acids 287 found to be 94.0% based on the iumaric acid used. 1. Pentaerythritol 108 The above materials are heated at about 220 C. until the desired acid number is attained. The resin has an acid number of 26.6 and a 50% solution in hydrogenatednaphtha solvent gives a viscosity of 14 poises.

Resin "D" Parts Isoprene fumaric adduct 184 Refined castor oil 60 Glycerine 95 Soya fatty acids 54 The above materials are charged into a kettle and heated at 220 C. until the desired acid numher is reached. The product is soluble in xylol giving a 50% solids content.

Resin "E Parts Phthalic anhydride 148 Isoprene-iumaric adduct 4 Refined castor oil 60 Soya fatty acids 54 Glycerine 94 The materials are all charged into a kettle and heated to 235 C. until a viscosity of about 13 poises is reached, and then heated at about 200 C. for about 2 hours. A 50% xylol solution of the final product has a viscosity of about 27 poises and an acid number of 10.2.

Resin F Parts Resin from Example 8 65 Butylated urea-formaldehyde resin. 35 Cobalt naphthenate 0.005 The above materials are mixed, then flowed out on panels and baked at 150 C. for /2 hour. The him has good mar-prooi. properties, good hardness, is tack free and has an exceptionally light color.

We claim: 1. A process for the preparation of fumaric acid adducts comprising reacting fumaric acid and at least one conjugated diene hydrocarbon in an aqueous medium in a closed vessel at a temperature between 100 and 200 C. until the reaction is substantially complete.

2. A process for the preparation of a fumaric acid-isoprene adduct comprising reacting fumaric acid and isoprene in an aqueous medium in a closed vesselat atemperature between 100 and 200 C. until the reaction is substantially complete.

3. A process for the preparation of a fumaric acid butadiene adduct comprising reacting fumaric acid and butadiene in an aqueous medium in a closed vessel at a temperature between 100 and 200 C.

.4. A process for the preparation of a fumaric acid-alloocimene adduct comprising reacting fumarlc acid and alloocimene in an aqueous medium in a closed vessel at a temperature between 100 and 200 C. until the reaction is substantially complete.

5. A fumaric acid-conjugated diene hydrocarbon adduct prepared according to the process disclosed in claim 1. v

6. A fumaric acid-isoprene adduct prepared according to the process or claim 2.

7. A fumaric acid-butadiene adduct prepared according to the process of claim 3.

8. A fumarlc acid-alloiicimene adduct prepared according to the process of claim 4.

CHARLES H. PARKER, JR. LESLIE C. LANE.

REFERENCES CITED file of this patent:

UNITED STATES PATENTS Number Name Date 1,944,731 Diels, et al. Jan. 23, 1934 1,967,862 Carothers, et al. July 24, 1934 1,978,062 Scheyer Oct. 23, 1934 1,993,037 Littman Mar. 5, 1935 2,039,243 Krzikalla, et al. Apr. 28, 1936 2,047,398 Voss, et al July 14, 1936 2,275,383 Soday Mar. 3, 1942 2,275,385 Soday Mar. 3, 1942 2,344,831 Ott Mar. 21, 1944 FOREIGN PATENTS Number Country Date 627,783 Germany Mar. 23, 1936 OTHER REFERENCES (Nordemann Publishing Co., 1938) pages -46. 

